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Patented June. 24, i93yd srrss eTENT' OFFER .rosm' sirens, or COLOGNE-MULHEIM, GERMANY, ASSIGNOR r0 I. e. rAnBEnmnn's'rarn AK'lIENGESELLSCHAFT, or FRANKFORT-ON-THE-MAIN, GERMANY, a conrona'rron or GERMANY 2-ARYIi-4.6-DIHYDR6XYPYRIMIDINES We Drawing. Application filed March 28, 1929, Serial No. 350,837, and in Germany April 3, 1928.

wherein R stands for an aromatic nucleus such as a naphthalene or benzene nucleus which aromatic nucleus may be substituted by any inonovalentsubstituents, for example by halogen, alkyl-, nitro-, am-ino-, carboxylic acidor sulfonic acid-groups.

According to the present invention 2-arylfi-dihydroxypyrimidines of the above for-' mula are obtainable by heating an-amidine of anularyl-carboxylic acid'of the general form a r Y wherein R stands for anaromatic nucleus which may be substituted by any monovalent substituents'with at least the molecular quan+ .tities of malonic acid diethyl ethertoan elevated temperature, say to. temperatures between 1506 C. and 250 C. for about one hour.

The process may be carried out in a highly boiling inert solvent such as nitrobenzene or advantageously malonic acid diethyles'ter. The process roc'eeds according to the following equation. The pyrimidines separate in a crystalline form during-the reactionand are filteredaft er cooling mended insoluble inalcohol, ether, acetone, mineral acids, soluble incaustic alkalies and inhot pyridine, they are yat ijiable intermediate products in the manufacture of dyestufis.

phenyl) 4-6 dihydroxypyriinidine by the in- 5, boiled while stirring for one hour with 50 -n-J bn+2oimon The invention is illustrated by the following examples but is not restricted thereto.

Example 1 ethylester. At first solution enters, then red- I dish-brown crystals precipitate which on further heating are transformed into the yellow colored pyrimidine of the, formula:

' on /N C NOF CH on After cooling it is filtered with suction and the 2-({l-nitrophenyl)'-4.6-dioxypyrimidine is obtained from pyridinein form of yellow-' ish' matted little needles which melt while bulging out at 320 C. The new derivative of pyrimidine is insoluble in alcohol, ether, acetone, mineral acids,

it is soluble in soda lye and in hot pyridine.

The filtrate obtained by the working up is available again for a new condensation process. Y

The 2 (4-nitrophenyl) -4.6-dich1oropyrimidine is obtainable from the 2.(4'-nitroteraction of phosphoroxychloride is after crystallizing from benzene in form of needles of melting point 266 'C. o

Instead of the el-m'trobenzamidine there may also be used the S-nitrobenzamidine with the same result.

- Example 2 g by weight of benzamidine are 12 parts parts'by weight of malonic acid-diethylesterl After cooling the 2-phenyl-4.6-dihydroxy-1 yrimidine has been separated in a crystal 7 I ma form; after recrystallization from glacial acetic acid, it has a melting point-of 325 05 y A second crystaliizationis found 7 by distilling part of the unchanged malonicester-j the yield of 2-phenyl-4.6-dihydroxy- .pyrlmidine amountsQto about 100% of the heo'ryusing the 4 or 3-methylbenza 100 midine, halogenated benzamidine, naphthoicacid amidine, etc., the corresponding pyrimidines are obtainable on the same way. I claim: 1 1. The process which comprises heating an amidine of an aryl-carboxylic acid of the general formula 3-0 NH: v

R C\NH:

wherein R stands for an aromatic nucleus which may be substituted by any monovalent substituents with at least the molecular quantity of malonic acid diethylester to a temperature of about 150 C. to about 250 C.

for about one hour.

3. The process which comprises heating an amidine of an aryl-carboxylic acid of the general formula wherein R stands for an aromatic nucleus which may be substituted by any monovalent substituent's with at least-the molecular quantity of malonic acid diethylester in a highly boiling organic solvent for about one hour. 4. The process which comprises heating an amidine of an aryl-carboxylic acid of the general formula n-c B wherein It stands for an aromatic nucleus which may be substituted by any monovalent substituents with at least the molecular quantity of malonic acid diethylester to a temperature of about 150 C. to about 250 C. for about one hour.

5. The process which comprises heating an a'midine of an aryl-carboxylic' acid of the general formula wherein :1: stands for hydrogen or any monovalentsubstituents with at least the molecular quantity of malonic acid diethylester to an elevated temperature for about one hdur.

6. The process which comprises heating an amidine of an a'ryl-carboxylic acid of the general formula wherein R stands for an aromatic nucleus which may be substituted by any monovalent substituents with at least the molecular quantity of malonic acid diethylester to a temperature of about 150 C. to about 250 C. for about one hour.

' wherein R stands for an aromatic nucleus which may be substituted by any monovalent substituent with at least the molecular quanti of malonic acid diethylester in a highly boiling organic solvent for about-one hour.

8. The process which comprises heating an amidine of an aryl-carboir'ylic acid of the general formula I wherein R stands for an aromatic nucleus which may be substituted by any monovalent substituents with at least the molecular quantity of malonic acid diethylester to a temperature of about 150; C. to about 250 C. for about one hour.

9. The process which comprises heating a benzamidine of the general formula I NH O N01 with malonic diethylester in excess to boiling for about one hour.

10. The process which comprises heating finely powdered 4-nitro-benzamidine in 300 parts by weight of malonic acid diethylester to boiling for about one hour while stirring. 11. As new'products the compounds of the following general formula 7 wherein R stands for an aromatic nucleus which is substituted by at least one monovalent substituent, being generally yellowish crystalline substances, insoluble in. alcohol, ether, acetone, mineral acids, soluble in canstic alkalies and in hot pyridine, and being valuable intermediate products in the manufacture of dyestufis.

weaves 12., As new products the compounds of the following general formula a t u r t ao-d :Lon

wherein m stands for a monovalent substituent, being generally yellowish crystalline substances, insoluble in alcohol, ether, acetone,

mineral acids, soluble in caustic alkalies and in hot pyridine, and-being valuable intermediate products in the manufacture of dyestuffs.

14. As new products the compounds of the following general formula being generally yellowish crystalline substances, insoluble in alcohol, ether, acetone, mineral acids soluble in caustic alkalies and in hot pyridine, and being valuable intermediate products in the manufacture of dye stufis.

15. As a new product the compound of the formula being a yellowish crystalline substance, melt- I my hand.

ing at 320 (3., being insoluble in alcohol, ether, acetone, mineral acids, solublein soda lye and in hot pyridine, and being a valuable,

intermediate product in the manufacture of dyestufi's.

In testimony whereof I have hereunto set aosnn HILGER. a

Certificatepf Correction Patent No. 1,766,748. Gra ted June 24, 1930. t5. JOSEF HILGER It is hereby certified that error appears in the printed specification of the'above numbered patent. requiring correction as follows: Page 2, lines 115 to 120, claim- 11, strike out the formula. and insert instead E K -B d-on and that the said Letter Patent should be read with this' correctibh ftherin'fl thh the same may conform to the record of the case in the Patent Ofliee.

- Signed and sealed this 19th day of August, A. D. 1930."=

[SEAL] I I 

